Unsaturated polymers of heterocyclic olefins

Abstract

Polymers having repeating units of the general formula I ##STR1## where Y and Z are the same or different and each denote --H, --COOR 1 or --CON(R 2 )R 3 , with the proviso that Y and Z do not both denote --H, or Y and Z together with the carbon atoms to which they are attached denote a divalent cyclic group of formula ##STR2## A denotes --O-- or --N(R 4 )--, R 1 denotes --H, C 1 -C 4 alkyl or C 2 -C 4 hydroxyalkyl, R 2 and R 3 each denote --H, C 1 -C 4 alkyl or C 1 -C 4 hydroxyalkyl, and R 4 denotes --H, --OH, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl or C 1 -C 4 alkoxy. The carboxyl-containing polymers are useful in water treatment.

We claim: 
     
       1. A polymer having a M w  of 500 to 10,000 of the formula ##STR6## where Y and Z are the same or different and each denote --H, --COOR 1  or --CON(R 2 )R 3 , with the proviso that Y and Z do not both denote --H, or Y and Z together with the carbon atoms to which they are attached denote a divalent cyclic group of formula ##STR7## wherein A denotes --O-- or --N(R 4 )--, R 1  denotes --H, C 1  -C 4  alkyl or C 2  -C 4  hydroxyalkyl, R 2  and R 3  each denote --H, C 1  -C 4  alkyl or C 1  -C 4  hydroxyalkyl, and R 4  denotes --H, --OH, C 1  -C 4  alkyl, C 1  -C 4  hydroxyalkyl or C 1  -C 4  alkoxy. 
     
     
       2. A polymer according to claim 1, in which at least one of Y and Z denotes --COOR 1  and R 1  denotes a hydrogen atom or group. 
     
     
       3. A polymer according to claim 1, in which Y and Z are the same and each denote --COOH or --COOCH 3 . 
     
     
       4. A process for the preparation of a polymer according to claim 1, which comprises ring opening metathesis polymerization of an olefin monomer of the formula III ##STR8## where Y and Z are defined in claim 1, in an aqueous or organic solvent or diluent in the presence, as catalyst, of a salt or complex of a metal of Group VIII of the Periodic Table and in the presence of a chain transfer agent of the formula IV   R.sup.5 --CH═CH--R.sup.6                               (IV)     where R 5  and R 6  are the same or different and each denote --H, C 1  -C 4  alkyl, phenyl, halophenyl, --CH 2  OR 1 , --COOR 1  or --CON(R 2 )R 3 , with the proviso that R 5  and R 6  are not both --H, where R 1 , R 2  and R 3  are as defined in claim 1.   
     
     
       5. A process according to claim 4, in which R 5  and R 6  are the same and denote --CH 2  OH or --COOH or in which R 5  denotes --H and R 6  denotes --COOH. 
     
     
       6. A process according to claim 4, in which the molar ratio of chain transfer agent to monomer is from 1:100 to 10:1. 
     
     
       7. A process according to claim 4, in which the catalyst is a salt or complex of ruthenium or osmium. 
     
     
       8. A process according to claim 7, in which the catalyst is a halide of ruthenium or osmium. 
     
     
       9. A process according to claim 8, in which the catalyst is ruthenium III chloride or osmium III chloride. 
     
     
       10. A process according to claim 4, which is carried out in water or a chlorobenzene-water mixture. 
     
     
       11. A process according to claim 4, which is carried out at a temperature of 40° to 80° C. 
     
     
       12. An aqueous composition containing from 0.1 to 50,000 ppm by weight of a polymer according to claim 1. 
     
     
       13. A composition according to claim 12, which contains from 0.1 to 100 ppm by weight of the polymer. 
     
     
       14. A method of treating an aqueous liquid which comprises adding to the liquid from 0.1 to 50,000 ppm by weight of a polymer according to claim 1. 
     
     
       15. A method according to claim 14, wherein said polymer contains carboxyl groups and is added as a scale control additive. 
     
     
       16. A method according to claim 15, wherein said polymer is added in an amount of 0.1 to 100 ppm by weight. 
     
     
       17. A method according to claim 15, wherein said polymer is added in an amount of 0.5 to 20 ppm by weight.